JP2011195736A - Polyimide precursor and photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide precursor and a photosensitive resin composition formable of a film exhibiting preferable developability, formable of a coverlay excellent in flame retardancy and insulation reliability, furthermore achievable of a flexible printed-wiring board small in warpage after firing.SOLUTION: This polyimide precursor containing a phosphorus atom includes a polyimide structure expressed by general formula (1) and a polyamic acid structure expressed by general formula (2) as recurring structural units, respectively; in formulae, -T- is a recurring structure of a siloxane unit; and Rand/or Rcontain(s) a phosphorus atom.

Description

  The present invention relates to a polyimide precursor containing a phosphorus atom, a photosensitive resin composition containing the polyimide precursor, a photosensitive film using the photosensitive resin composition, and a substrate obtained using the photosensitive film. And a laminate thereof.

  In recent years, a film-like printed circuit board called a flexible printed circuit board (hereinafter also referred to as “FPC”) has gained popularity. This board has a structure with a coverlay made of polyimide film etc. on a processed FCCL (Flexible Copper Clad Laminate) and is mainly used for equipment such as mobile phones, notebook computers, digital cameras, etc. It has been. Since FPC maintains its function even when it is bent, it is an indispensable material for reducing the size and weight of equipment. Particularly in recent years, electronic devices represented by notebook computers have been reduced in size and weight. By adopting FPC for such products, the size and weight of the devices are reduced, the product cost is reduced, and the design is reduced. Contributes to simplification.

  Development of photosensitive coverlays has been vigorously performed for fine processing by lithography for miniaturization and thinning of FPC. Among these, a photosensitive coverlay using a polyimide precursor is expected as an excellent coverlay from the viewpoint of bending resistance derived from polyimide, heat resistance, electrical insulation, and flame retardancy.

  In addition, in conventional screen printing, the photosensitive resin composition is used from the viewpoints of problems such as the solvent removal process and the double-sided processing, and the resolution of screen printing is low. It is desired to form a dry film.

  Among these, various developments have been vigorously performed especially for the flame retardancy of polyimide precursors (see Patent Documents 1 to 4 and Non-Patent Document 1). In Patent Document 1, although flame retardancy is improved by adding a flame retardant containing a phosphorus atom, when a photosensitive resin composition is used, the photosensitive characteristics and the insulation reliability tend to be remarkably lowered. In addition, Patent Document 2 discloses a negative photosensitive resin composition containing a phosphorus atom-containing ethylenically unsaturated compound as an example of improving photosensitive characteristics, but although insulation reliability tends to be improved, Photosensitivity characteristics tend to be insufficient, and tend to warp after curing. Patent Document 3 and Non-Patent Document 1 disclose phosphorus atom-containing polyimide precursors for the purpose of improving flame retardancy and heat resistance, but do not disclose photosensitivity. Moreover, in patent document 4, although the polyimide precursor containing the phosphorus atom which has photosensitivity is disclosed, although the resin composition which has photosensitivity is obtained, it exists in the tendency which warps after baking.

JP 2008-304569 A JP 2008-209502 A JP 2009-221309 A JP 2010-1433 A

Polymer, vol. 43 (6), 1773-1779 (2002)

  The present invention has been made in view of the above points, can form a film showing good developability, can form a coverlay excellent in flame retardancy and insulation reliability, and warps after firing. It aims at providing the polyimide precursor and photosensitive resin composition which can implement | achieve a flexible printed wiring board with few.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by a polyimide precursor containing a phosphorus atom and having a predetermined repeating structure, and a photosensitive resin composition containing the polyimide precursor. It came to complete. That is, the present invention is as follows.

（式（１）の−Ｔ−は、一般式（３）及び／又は一般式（４）を表す。式（１）、式（２）、式（３）、式（４）中、Ｒ_１、Ｒ_２、Ｒ_４、Ｒ_５、Ｒ_７、Ｒ_８、Ｒ_１０、Ｒ_１１、Ｒ_１３、Ｒ_１４はそれぞれ独立して水素原子又は炭素数１〜炭素数２０の１価の有機基を表し、同じであっても異なっていても良い。Ｒ_３、Ｒ_６、Ｒ_９、Ｒ_１２、Ｒ_１５は炭素数１〜炭素数２０の４価の有機基を表し、ｍ、ｎ、ｐはそれぞれ独立して０以上１００以下の整数を表す。Ｒ_１６はテトラカルボン酸二無水物に由来する４価の有機基を表し、Ｒ_１７は炭素数１〜炭素数９０の２価の有機基を表し、Ｒ_１６及び／又はＲ_１７はリン原子を含有する。Ｒ_１８は炭素数１〜炭素数３０の２価の有機基、Ｒ_１９は炭素数１〜炭素数３０の１価の有機基、ｑは１以上３０以下の整数を表す。） The polyimide precursor of the present invention is a polyimide precursor containing a phosphorus atom, and includes a polyimide structure represented by the following general formula (1) and a polyamic acid structure represented by the following general formula (2). It is characterized by having each as a repeating structural unit.

(-T- in Formula (1) represents General Formula (3) and / or General Formula (4). In Formula (1), Formula (2), Formula (3), and Formula (4), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ₃ , R ₆ , R ₉ , R ₁₂ , and R ₁₅ represent a tetravalent organic group having 1 to 20 carbon atoms, and m, n, and p are respectively Independently represents an integer of 0 to 100. R ₁₆ represents a tetravalent organic group derived from tetracarboxylic dianhydride, and R ₁₇ represents a divalent organic group having 1 to 90 carbon atoms. , R ₁₆ and / or R ₁₇ contain a phosphorus atom, R ₁₈ is a divalent organic group having 1 to 30 carbon atoms, and R ₁₉ is 1 having 1 to 30 carbon atoms. A valent organic group, q represents an integer of 1-30.)

（式（５）中、Ｒ_１、Ｒ_２、Ｒ_４、Ｒ_５、Ｒ_７、Ｒ_８、Ｒ_１０、Ｒ_１１、Ｒ_１３、Ｒ_１４はそれぞれ独立して水素原子又は炭素数１〜炭素数２０の１価の有機基を表し、同じであっても異なっていても良い。Ｒ_３、Ｒ_６、Ｒ_９、Ｒ_１２、Ｒ_１５は炭素数１〜炭素数２０の４価の有機基を表し、ｍ、ｎ、ｐはそれぞれ独立して０以上１００以下の整数を表す。Ｒ_１６はテトラカルボン酸二無水物に由来する４価の有機基を表し、Ｒ_１７は炭素数１〜炭素数９０の２価の有機基を表し、Ｒ_１６及び／又はＲ_１７はリン原子を含有する。Ａ、Ｂ、Ｃは各単位のｍｏｌ％を表し、０．０５≦Ｃ／（Ａ＋Ｂ＋Ｃ）≦０．９５を満たす。） In the polyimide precursor of this invention, it is preferable that the structure represented by following General formula (5) is included.

(In the formula (5), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ are each independently a hydrogen atom or carbon number 1 to carbon number. Represents a monovalent organic group of 20, which may be the same or different, and R ₃ , R ₆ , R ₉ , R ₁₂ , and R ₁₅ represent a tetravalent organic group having 1 to 20 carbon atoms. M, n and p each independently represents an integer of 0 to 100. R ₁₆ represents a tetravalent organic group derived from tetracarboxylic dianhydride, and R ₁₇ represents a carbon number of 1 to carbon. 90 represents a divalent organic group of 90, R ₁₆ and / or R ₁₇ contains a phosphorus atom, A, B, and C represent mol% of each unit, and 0.05 ≦ C / (A + B + C) ≦ 0. 95 is satisfied.)

（式（６）中、Ｒ_１６はテトラカルボン酸二無水物に由来する炭素数１〜炭素数５０の４価の有機基、Ｒ_１８は炭素数１〜炭素数３０の２価の有機基、Ｒ_１７は炭素数１〜炭素数９０の２価の有機基、Ｒ_１９は炭素数１〜炭素数３０の１価の有機基、ｑは１以上３０以下の整数を表し、Ｒ_１６及び／又はＲ_１７はリン原子を含有する。Ｘ、Ｙ、Ｚは各単位のｍｏｌ％を表し、０．０５≦Ｚ／（Ｘ＋Ｙ＋Ｚ）≦０．９５を満たす。） In the polyimide precursor of this invention, it is preferable that the structure represented by following General formula (6) is included.

(In the formula (6), R ₁₆ is a tetravalent organic group having 1 to 50 carbon atoms derived from tetracarboxylic dianhydride, R ₁₈ is a divalent organic group having 1 to 30 carbon atoms, R ₁₇ is a divalent organic group having 1 to 90 carbon atoms, R ₁₉ is a monovalent organic group having 1 to 30 carbon atoms, q is an integer of 1 to 30, and R ₁₆ and / or R ₁₇ contains a phosphorus atom, and X, Y, and Z represent mol% of each unit and satisfy 0.05 ≦ Z / (X + Y + Z) ≦ 0.95.)

（式（７）、式（８）中、Ｒ_２０、Ｒ_２１、Ｒ_２２、Ｒ_２３は水素原子又は炭素数１〜炭素数２０以下の１価の有機基を表す。Ａｒは炭素数５以上炭素数２０以下の芳香族化合物に由来する２価の有機基を表す。） The polyimide precursor of the present invention is preferably composed of an acid dianhydride represented by the following general formula (7) and / or the following general formula (8).

(In Formula (7) and Formula (8), R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Ar represents 5 or more carbon atoms. Represents a divalent organic group derived from an aromatic compound having 20 or less carbon atoms.)

（式（９）〜式（１３）中、Ｒ_２４、Ｒ_２５、Ｒ_２６、Ｒ_２７、Ｒ_２８、Ｒ_２９、Ｒ_３０、Ｒ_３１、Ｒ_３２、Ｒ_３３、は水素原子又は炭素数１〜炭素数２０の１価の有機基を表す。） In the polyimide precursor of this invention, it is preferable to be comprised from the at least 1 diamine selected from the group which consists of following General formula (9)-following General formula (13).

(In the formulas (9) to (13), R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ are a hydrogen atom or a carbon number 1 to 1 Represents a monovalent organic group having 20 carbon atoms.)

  The photosensitive resin composition of this invention contains the said polyimide precursor and a photosensitive agent, It is characterized by the above-mentioned.

  In the photosensitive resin composition of this invention, it is preferable that the said photosensitive agent contains the (meth) acrylate compound which has at least 2 unsaturated double bond which can be photopolymerized, and a photoinitiator.

  In the photosensitive resin composition of the present invention, the (meth) acrylate compound having at least two unsaturated double bonds capable of photopolymerization has a compound having two double bonds and three or more double bonds. It is preferable that both are included.

  In the photosensitive resin composition of the present invention, the photosensitive agent is preferably a quinonediazide compound.

  The photosensitive resin composition of the present invention preferably contains a phosphorus compound.

  In the photosensitive resin composition of the present invention, the phosphorus compound preferably has at least one structure selected from the group consisting of a phosphate ester structure and a phosphazene structure.

  The photosensitive film of this invention is characterized by including the said photosensitive resin composition and a support film layer.

  In the photosensitive film of this invention, it is preferable to have a carrier film in the one side whole surface.

  The photosensitive film of the present invention preferably includes a cover film.

  The cover lay of the present invention is obtained by imidizing the photosensitive resin composition.

  The flexible printed wiring board of the present invention is obtained by imidizing the photosensitive resin composition on the substrate.

  The laminated body of this invention is comprised from the said coverlay and a copper clad laminated board, It is characterized by the above-mentioned.

  According to the present invention, a photosensitive film capable of forming a film showing good developability, forming a coverlay excellent in flame retardancy and insulation reliability, and realizing a flexible printed wiring board with less warping after firing. A functional resin composition can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
The polyimide precursor which concerns on this invention is a phosphorus atom containing polyimide precursor containing a phosphorus atom, and has a predetermined repeating structure. Moreover, the polyimide precursor which concerns on this invention can be used as a photosensitive resin composition by addition of various additives, such as a photosensitive agent.

(A) Phosphorus atom-containing polyimide precursor As the phosphorus atom-containing polyimide precursor, a polyimide structure represented by the following general formula (1) and a polyamic acid structure represented by the following general formula (2) are repeated. There is no limitation as long as it has a structural unit. By using those having these structures, warpage after firing is good, and a decrease in weight average molecular weight during film formation can be suppressed.

（式（１）の−Ｔ−は、一般式（３）及び／又は一般式（４）を表す。式（１）、式（２）、式（３）、式（４）中、Ｒ_１、Ｒ_２、Ｒ_４、Ｒ_５、Ｒ_７、Ｒ_８、Ｒ_１０、Ｒ_１１、Ｒ_１３、Ｒ_１４はそれぞれ独立して水素原子又は炭素数１〜炭素数２０の１価の有機基を表し、同じであっても異なっていても良い。Ｒ_３、Ｒ_６、Ｒ_９、Ｒ_１２、Ｒ_１５は炭素数１〜炭素数２０の４価の有機基を表し、ｍ、ｎ、ｐはそれぞれ独立して０以上１００以下の整数を表す。Ｒ_１６はテトラカルボン酸二無水物に由来する４価の有機基を表し、Ｒ_１７は炭素数１〜炭素数９０の２価の有機基を表し、Ｒ_１６及び／又はＲ_１７はリン原子を含有する。Ｒ_１８は炭素数１〜炭素数３０の２価の有機基、Ｒ_１９は炭素数１〜炭素数３０の１価の有機基、ｑは１以上３０以下の整数を表す。）

(-T- in Formula (1) represents General Formula (3) and / or General Formula (4). In Formula (1), Formula (2), Formula (3), and Formula (4), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ₃ , R ₆ , R ₉ , R ₁₂ , and R ₁₅ represent a tetravalent organic group having 1 to 20 carbon atoms, and m, n, and p are respectively Independently represents an integer of 0 to 100. R ₁₆ represents a tetravalent organic group derived from tetracarboxylic dianhydride, and R ₁₇ represents a divalent organic group having 1 to 90 carbon atoms. , R ₁₆ and / or R ₁₇ contain a phosphorus atom, R ₁₈ is a divalent organic group having 1 to 30 carbon atoms, and R ₁₉ is 1 having 1 to 30 carbon atoms. A valent organic group, q represents an integer of 1-30.)

Further, the polyimide structure represented by the above general formula (1), and the polyamic acid structure represented by the above general formula (2), the phosphorus atom-containing polyimide precursor having a repeating structural unit each, R ₁₆ and / or is not limited as long as it contains a phosphorus atom in R _17, a tetracarboxylic dianhydride represented by the following general formula (7) is represented by the following general formula (14) and / or (15) A structure obtained by polymerizing and cyclizing the diamine and then polymerizing the diamine represented by the following general formula (16) is more preferable from the viewpoint of developability.

（式（７）、式（１４）、式（１５）、式（１６）中、Ｒ_１、Ｒ_２、Ｒ_４、Ｒ_５、Ｒ_７、Ｒ_８、Ｒ_１０、Ｒ_１１、Ｒ_１３、Ｒ_１４はそれぞれ独立して水素原子又は炭素数１〜炭素数２０の１価の有機基を表し、同じであっても異なっていても良い。Ｒ_３、Ｒ_６、Ｒ_９、Ｒ_１２、Ｒ_１５は炭素数１〜炭素数２０の４価の有機基を表し、ｍ、ｎ、ｐはそれぞれ独立して０以上１００以下の整数を表す。Ｒ_１７は炭素数１〜炭素数９０の２価の有機基を表す。Ｒ_２０、Ｒ_２１は水素原子又は炭素数１〜炭素数２０以下の１価の有機基を表す。Ａｒは炭素数５以上炭素数２０以下の芳香族化合物に由来する２価の有機基を表す。Ｒ_１８は炭素数１〜炭素数３０の２価の有機基、Ｒ_１９は炭素数１〜炭素数３０の１価の有機基、ｑは１以上３０以下の整数を表す。）

(Equation (7), equation (14), wherein (15), equation _{(16), R 1, R} 2, R 4, R 5, R 7, R 8, R 10, R 11, R 13, R ₁₄ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and may be the same or different from each other R ₃ , R ₆ , R ₉ , R ₁₂ , R ₁₅ Represents a tetravalent organic group having 1 to 20 carbon atoms, and m, n, and p each independently represent an integer of 0 to 100. R ₁₇ is a divalent organic group having 1 to 90 carbon atoms. Represents an organic group, R ₂₀ and R ₂₁ represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and Ar represents a divalent aromatic compound having 5 to 20 carbon atoms. R ₁₈ is a divalent organic group having 1 to 30 carbon atoms, R ₁₉ is a monovalent organic group having 1 to 30 carbon atoms, q represents an integer of 1-30.

（式（５）、式（６）中、Ｒ_１、Ｒ_２、Ｒ_４、Ｒ_５、Ｒ_７、Ｒ_８、Ｒ_１０、Ｒ_１１、Ｒ_１３、Ｒ_１４はそれぞれ独立して水素原子又は炭素数１〜炭素数２０の１価の有機基を表し、同じであっても異なっていても良い。Ｒ_３、Ｒ_６、Ｒ_９、Ｒ_１２、Ｒ_１５は炭素数１〜炭素数２０の４価の有機基を表し、ｍ、ｎ、ｐはそれぞれ独立して０以上１００以下の整数を表す。Ｒ_１６は上記一般式（２）に由来する４価の有機基を表し、Ｒ_１７は炭素数１〜炭素数９０の２価の有機基を表す。Ａ、Ｂ、Ｃは各単位のｍｏｌ％を表し、０．０５≦Ｃ／（Ａ＋Ｂ＋Ｃ）≦０．９５を満たす。Ｒ_１８は炭素数１〜炭素数３０の２価の有機基、Ｒ_１９は炭素数１〜炭素数３０の１価の有機基、ｑは１以上３０以下の整数を表す。Ｘ、Ｙ、Ｚは各単位のｍｏｌ％を表し、０．０５≦Ｚ／（Ｘ＋Ｙ＋Ｚ）≦０．９５を満たす。） Among the above structures, the phosphorus atom-containing polyimide precursor is particularly preferably a structure represented by the following general formula (5) and / or (6) from the viewpoint of developability.

(In Formula (5) and Formula (6), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ are each independently a hydrogen atom or carbon. Represents a monovalent organic group having 1 to 20 carbon atoms, and may be the same or different, and R ₃ , R ₆ , R ₉ , R ₁₂ and R ₁₅ are 4 having 1 to 20 carbon atoms. M, n, and p each independently represents an integer of 0 to 100. R ₁₆ represents a tetravalent organic group derived from the general formula (2), and R ₁₇ represents carbon. Represents a divalent organic group having 1 to 90 carbon atoms, A, B, and C represent mol% of each unit and satisfy 0.05 ≦ C / (A + B + C) ≦ 0.95, and R ₁₈ represents carbon number. 1-2 monovalent organic group 30 carbon _{atoms, R 19} is a monovalent organic group of 30 carbon 1 carbon carbon atoms, q is an integer of 1 to 30 .X, Y Z represents a mol% of the unit satisfies 0.05 ≦ Z / (X + Y + Z) ≦ 0.95.)

  In the phosphorus atom-containing polyimide precursor represented by the general formula (5), from the viewpoint of developability, a structure in the range of 0.1 ≦ C / (A + B + C) ≦ 0.9 is preferable, and 0.1 ≦ C / A structure in the range of (A + B + C) ≦ 0.8 is more preferable, and a structure in the range of 0.2 ≦ C / (A + B + C) ≦ 0.75 is most preferable. If 0.1 ≦ C / (A + B + C), good developability is exhibited, and if C / (A + B + C) ≦ 0.9, good warpage is exhibited after firing.

  In addition, in the phosphorus atom-containing polyimide precursor represented by the general formula (6), from the viewpoint of developability, a structure in a range of 0.1 ≦ Z / (X + Y + Z) ≦ 0.9 is preferable, and 0.1 ≦ A structure having a range of Z / (X + Y + Z) ≦ 0.8 is more preferable, and a structure having a range of 0.1 ≦ Z / (X + Y + Z) ≦ 0.75 is most preferable. If 0.1 ≦ Z / (X + Y + Z), good developability is shown, and if Z / (X + Y + Z) ≦ 0.9, good warpage is exhibited after firing.

Examples of the phosphorus atom-containing tetracarboxylic acid in the present invention include structures represented by the following general formula (7) and / or the following general formula (8).

As tetracarboxylic dianhydride represented by the general formulas (7) and (8), R ₂₀ , R ₂₁ , R ₂₂ , and R ₂₃ are a hydrogen atom or a monovalent having 1 to 20 carbon atoms. It represents an organic group, and Ar is not limited as long as it has a structure representing a divalent organic group derived from an aromatic compound having 5 to 20 carbon atoms. From the viewpoint of flame retardancy and developability, Ar is not limited. Is preferably a divalent organic group derived from benzene, naphthalene or anthracene.

  Examples of the diamine containing a phosphorus atom in the present invention include structures represented by the following general formula (9) to the following general formula (13).

（式（９）〜式（１３）におけるＲ_２４、Ｒ_２５、Ｒ_２６、Ｒ_２７、Ｒ_２８、Ｒ_２９、Ｒ_３０、Ｒ_３１、Ｒ_３２、Ｒ_３３は水素原子又は炭素数１〜炭素数２０の１価の有機基を表す。）

(R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , and R ₃₃ in formula (9) to formula (13) are a hydrogen atom or a carbon number of 1 to carbon atoms. 20 represents a monovalent organic group.)

In the general formula (9) to the general formula (13), R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , and R ₃₃ are from the viewpoint of developability. To a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.

  The diamine represented by the general formula (14) is not limited as long as it has the structure represented by the general formula (14), but may be 1,8-diamino-3,6-dioxyoctane or the like. Polyoxyethylenediamine compounds, polyoxyalkylenediamine compounds such as Huntsman's Jeffermine EDR-148 and EDR-176, polyoxypropylenediamine compounds such as Jeffamine D-230, D-400, D-2000, and D-4000, Examples thereof include compounds having different oxyalkylene groups such as HK-511, ED-600, ED-900, ED-2003, and XTJ-542. Among them, XTJ-542 is preferable from the viewpoint of warping after curing.

  The skeleton having these oxyalkylene groups can reduce the warpage of FPC after baking of polyimide, and m, n, and p are each independently an integer of 0 or more and 100 or less. 3 ≦ (m + n + p) ≦ 200 is preferable, and 3 ≦ (m + n + p) ≦ 150 is more preferable. In addition, by using the phosphorus atom-containing polyimide and / or the phosphorus atom-containing polyimide precursor in combination with the diamine represented by the general formula (14), the flame retardancy and the effect of reducing the warpage of the FPC after firing the polyimide can be obtained. Since it can exhibit together, it is preferable.

  The diamine represented by the general formula (15) is not limited as long as it has the structure represented by the general formula (15). For example, silicone diamine (manufactured by Shin-Etsu Chemical Co., Ltd., PAM-E, KF-8010, X-22-161A, X-22-1660B-3) and the like. It is preferable to use these diamines since the warpage after curing can be further improved.

  Examples of the diamine represented by the general formula (16) include 1,3-bis (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy). ) Alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3, 3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 3, 7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzo Enone, 4,4′-bis (4-aminophenyl) sulfide, 4,4′-diaminobenzanilide, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [ 2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-aminophenyl) fluorene, 5-amino-1- (4-aminomethyl) -1,3,3-trimethylindane, 1,4 -Bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene (hereinafter abbreviated as APB), 4,4'-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, trimethylene-biphenyl (4-aminobenzoate), 2,2-bis (4-aminophenoxyphenyl) propane, 4-aminophenyl-4-aminobenzoate, 2-methyl-4-aminophenyl-4-aminobenzoate, bis [4- ( 4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1-amino-3-amino Methyl-3,5,5-trimethylcyclohexane, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 3,5-diaminobenzoic acid, 3,3′-dihydroxy-4,4′-diaminobiphenyl, Examples thereof include diamine having a substituent such as 1,3-bis (4-aminophenoxybenzene). Among these, APB and 2,2-bis (4-aminophenoxyphenyl) propane are preferable from the viewpoint of realizing a low Tg (glass transition point) of the polyimide precursor and developability.

  In the present invention, the phosphorus atom-containing polyimide precursor is preferably composed of a tetracarboxylic dianhydride represented by the general formula (7) and / or the general formula (8). Carboxylic dianhydrides can be included. Other tetracarboxylic dianhydrides include pyromellitic anhydride, oxydiphthalic dianhydride, biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4. '-Tetracarboxylic dianhydride, diphenylsulfone-3,3', 4,4'-tetracarboxylic dianhydride, 4,4 '-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, Meta-terphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2,2,2] oct-7- Ene-2,3,5,6-tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclopentatricarboxylic acid- , 6: 3,5-dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, ethylene glycol bis (trimellitic acid monoester anhydride), p-phenylene bis (trimerit Acid monoester acid anhydride), pentanediol bis (trimellitic acid monoester acid anhydride), decanediol bis (trimellitic acid monoester acid anhydride), and the like.

  The phosphorus atom-containing polyimide precursor according to the present invention is effective even when used as a negative photosensitive resin composition or as a positive photosensitive resin composition.

  The main chain terminal of the phosphorus atom-containing polyimide precursor is not particularly limited as long as it does not affect the performance. A terminal derived from an acid dianhydride or a diamine used when producing a phosphorus atom-containing polyimide precursor may be used, or the terminal may be sealed with another acid anhydride, an amine compound, or the like.

  The phosphorus atom-containing polyimide precursor preferably has a weight average molecular weight of 1,000 or more and 1,000,000 or less. Here, the weight average molecular weight refers to a molecular weight measured by gel permeation chromatography using polystyrene having a known weight average molecular weight as a standard. The weight average molecular weight is preferably 1000 or more from the viewpoint of the strength of the polyimide film. Moreover, it is preferable that it is 1000000 or less from a viewpoint of the viscosity of a polyimide containing resin composition and a moldability. The weight average molecular weight is more preferably from 5,000 to 500,000, particularly preferably from 10,000 to 300,000, and most preferably from 25,000 to 50,000.

  It does not specifically limit as a manufacturing method of the phosphorus atom containing polyimide precursor in this invention. Then, a manufacturing method is demonstrated to the example of the case of the phosphorus atom containing polyimide precursor which has a polyimide structure and a polyamic acid structure based on this invention as a repeating unit, respectively. The phosphorus atom-containing polyimide precursor having each of the polyimide structure and the polyamic acid structure as a repeating unit according to the present invention reacts the acid dianhydride and diamine in a non-equal molar amount to form a first-stage polyimide structure (polyimide site). It can be produced by the step of synthesizing (step 1), and then the step of synthesizing the second stage polyamic acid structure (polyamic acid moiety) (step 2). Hereinafter, each process will be described.

(Process 1)
The process of synthesizing the first-stage polyimide site will be described. The step of synthesizing the first-stage polyimide site is not particularly limited, and a known method can be applied. More specifically, it is obtained by the following method. First, diamine is dissolved and / or dispersed in a polymerization solvent, acid dianhydride powder is added thereto, a solvent azeotroped with water is added, and a by-product water is removed azeotropically using a mechanical stirrer. The mixture is heated and stirred for 5 hours to 96 hours, preferably 0.5 hours to 30 hours. In this case, the monomer concentration is 0.5% by mass or more and 95% by mass or less, preferably 1% by mass or more and 90% by mass or less.

  When a polyimide site is synthesized, it can be obtained by adding a known imidization catalyst or without a catalyst. The imidization catalyst is not particularly limited, but an acid anhydride such as acetic anhydride, a lactone compound such as γ-valerolactone, γ-butyrolactone, γ-tetronic acid, γ-phthalide, γ-coumarin, and γ-phthalido acid, Examples thereof include tertiary amines such as pyridine, quinoline, N-methylmorpholine, and triethylamine. Moreover, 1 type or 2 or more types of mixtures may be sufficient as needed. Among these, a mixed system of γ-valerolactone and pyridine and a non-catalyst are particularly preferable from the viewpoint of high reactivity and influence on the next reaction.

  The amount of the imidization catalyst added is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less with respect to 100 parts by mass of the polyamic acid.

  The reaction solvent used in the synthesis of the polyimide moiety includes 2 to 9 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. Ether compounds of: ketone compounds having 2 to 6 carbon atoms such as acetone and methyl ethyl ketone; saturated compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decalin Hydrocarbon compounds; aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as benzene, toluene, xylene, mesitylene, tetralin; methyl acetate, ethyl acetate Ester compounds such as γ-butyrolactone and methyl benzoate having 3 to 12 carbon atoms; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride and 1,2-dichloroethane; acetonitrile N, N-dimethylformamide, N, N-dimethylacetamide, nitrogen-containing compounds having 2 to 10 carbon atoms such as N-methyl-2-pyrrolidone; and sulfur-containing compounds such as dimethyl sulfoxide. These may be one kind or a mixture of two or more kinds as necessary. Particularly preferable solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 12 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and carbon atoms having 2 to carbon atoms. A nitrogen-containing compound of several tens or less is mentioned. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.

  In the synthesis of the polyimide site, the reaction temperature is preferably 15 ° C. or higher and 250 ° C. or lower. If it is 15 degreeC or more, reaction will be started, and if it is 250 degrees C or less, there will be no deactivation of a catalyst. Preferably they are 20 degreeC or more and 220 degrees C or less, More preferably, they are 20 degreeC or more and 200 degrees C or less. The time required for the reaction varies depending on the purpose or reaction conditions, but is usually within 96 hours, particularly preferably in the range of 30 minutes to 30 hours.

(Process 2)
Next, the process for synthesizing the second stage polyamic acid moiety will be described. The synthesis of the polyamic acid moiety in the second step can be polymerized by adding the diamine and / or acid dianhydride using the polyimide moiety obtained in Step 1 as a starting material.

  The polymerization temperature in the synthesis of the second stage polyamic acid moiety is preferably 0 ° C. or higher and 250 ° C. or lower, more preferably 0 ° C. or higher and 100 ° C. or lower, and particularly preferably 0 ° C. or higher and 80 ° C. or lower.

  The time required for the reaction for synthesizing the polyamic acid moiety varies depending on the reaction conditions, but is usually within 96 hours, particularly preferably in the range of 30 minutes to 30 hours.

  As the reaction solvent, the same solvent as used for the production of the polyimide moiety in Step 1 can be used. In that case, the reaction solution of step 1 can be used as it is. Moreover, you may use the solvent different from what was used for manufacture of a polyimide site | part.

  Examples of such solvents include ether compounds having 2 to 9 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; acetone, methyl ethyl ketone, and the like. A ketone compound having 2 to 6 carbon atoms; a saturated hydrocarbon compound having 5 to 10 carbon atoms, such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, decalin; benzene, toluene, xylene Aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as mesitylene and tetralin; methyl acetate, ethyl acetate, γ-butyrolactone, benzoic acid Ester compounds having 3 to 12 carbon atoms such as chill; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride and 1,2-dichloroethane; acetonitrile, N, N-dimethylformamide N, N-dimethylacetamide, N-methyl-2-pyrrolidone and other nitrogen-containing compounds having 2 to 10 carbon atoms; sulfur-containing compounds such as dimethyl sulfoxide.

  These may be one kind or a mixture of two or more kinds as necessary. Particularly preferable solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 12 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and carbon atoms having 2 to carbon atoms. A nitrogen-containing compound of several tens or less is mentioned. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.

  The polyimide precursor after the production may be used as it is dissolved in the reaction solvent, or may be recovered and purified by the following method. The polyimide precursor after the production can be recovered by distilling off the solvent in the reaction solution under reduced pressure.

  Examples of the method for purifying the polyimide precursor include a method of removing insoluble acid dianhydride and diamine in the reaction solution by vacuum filtration, pressure filtration, or the like. Moreover, the purification method by what is called reprecipitation which adds a reaction solution to a poor solvent and precipitates can be implemented. Further, when a highly pure polyimide precursor is required, an extraction method by a carbon dioxide supercritical method is also possible.

(B) Photosensitive agent The photosensitive resin composition which concerns on this invention contains the said phosphorus atom containing polyimide precursor and a photosensitive agent. Here, the photosensitive agent represents a compound having a property that the structure is changed by light irradiation and the solubility in a solvent is changed. Examples of such a compound include a so-called positive type photosensitive agent in which a light irradiation site is dissolved and a so-called negative type photosensitizing agent in which the light irradiation site is insoluble.

  Examples of the negative photosensitive agent include (B-1) a combination of a (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds and (C) a photopolymerization initiator.

(B-1) (Meth) acrylate compound having two or more photopolymerizable unsaturated double bonds As (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds, tricyclodecanedi Methylol diacrylate, ethylene oxide (EO) modified bisphenol A dimethacrylate, EO modified hydrogenated bisphenol A diacrylate, 1,6-hexanediol (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di ( (Meth) acrylate, polyethylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropiate Lutrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether (meth) acrylate, bisphenol A diglycidyl ether di (meth) Acrylate, β-hydroxypropyl-β ′-(acryloyloxy) -propyl phthalate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate And pentaerythritol tri / tetra (meth) acrylate. Among them, from the viewpoint of warping after firing, EO-modified bisphenol A dimethacrylate, EO-modified hydrogenated bisphenol A diacrylate, and pentaerythritol tri / tetra (meth) acrylate are preferable. Further, it is preferable that the photosensitizer contains both a compound having two photopolymerizable double bonds and a compound having three or more double bonds. The amount of the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds is from 5 parts by weight to 60 parts by weight from the viewpoint of developability when the amount of the polyimide precursor is 100 parts by weight. Is preferably 10 parts by mass or more and 40 parts by mass or less.

(C) Photopolymerization initiator Examples of the photopolymerization initiator include benzyldimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one, benzyldipropyl ketals, benzyldiphenyl ketals, and benzoin. Methyl ethers, benzoin ethyl ether, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-isopropylthioxanthone, 2-fluorothioxanthone, 4-fluorothioxanthone 2-chlorothioxanthone, 4-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, benzophenone, 4,4′-bis (dimethylamino) benzophenone [Michler's ketone], 4,4′- Aromatic ketone compounds such as su (diethylamino) benzophenone, 2,2-dimethoxy-2-phenylacetophenone, triarylimidazole dimers such as lophine dimer, acridine compounds such as 9-phenylacridine, α, α-dimethoxy Oxime ester compounds such as α-morpholino-methylthiophenylacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, N-aryl-α-amino acid, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid, p- Diethylaminobenzoic acid, p-diisopropylaminobenzoic acid, p-benzoic acid ester, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-Hydro Xyloxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4-[(2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2 Α-hydroxyalkylphenones such as methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- (dimethylamino) -2- [ Α-aminoalkylphenones such as (4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis Acylphosphine oxides such as (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1,2-octyl Tandione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O Oxime esters such as -acetyloxime). Among these, oxime esters are preferable from the viewpoint of sensitivity.

  When the amount of the polyimide precursor is 100 parts by mass, the amount of the photopolymerization initiator is preferably 0.01 parts by mass or more and 40 parts by mass or less from the viewpoint of sensitivity and resolution. 0.5 parts by mass or more and 35 parts by mass or less are more preferable.

(B-2) Quinonediazide compound Examples of the compound exhibiting positive photosensitivity include compounds containing a quinonediazide structure, aromatic diazonium salt compounds, and compounds having an azide structure. From the viewpoint of solubility contrast, a compound containing a quinonediazide structure is preferred.

  Examples of the compound containing a quinonediazide structure include 1,2-benzoquinonediazidesulfonic acid esters, 1,2-benzoquinonediazidesulfonic acid amides, 1,2-naphthoquinonediazidesulfonic acid esters, 1,2-naphthoquinonediazidesulfonic acid. Amides are mentioned. Specifically, for example, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfone Acid esters, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, etc. 1,2-naphthoquinone diazide sulfonic acid esters of trihydroxybenzophenones; 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2 ′, 4, 4'-tetrahydroxybenzophenone-1,2-naphthoquino Diazide-5-sulfonic acid ester, 2,2 ′, 4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ′, 3 ′, 4-tetrahydroxybenzophenone-1 , 2-Naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone -1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2 ′, 3,4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ′, 3,4-tetra Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2 3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2 -1,2-naphthoquinone diazide sulfonic acid esters of tetrahydroxybenzophenones such as naphthoquinone diazide-5-sulfonic acid ester; 2,2 ', 3,4,6'-pentahydroxybenzophenone-1,2-naphthoquinone diazide- 1,2-naphthoquinone diazide sulfonic acid esters of pentahydroxybenzophenones such as 4-sulfonic acid ester, 2,2 ′, 3,4,6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester Class: 2, 3 ', 4, 4', 5 ', 6-hex Sahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3 ′, 4,4 ′, 5 ′, 6-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3 , 3 ′, 4,4 ′, 5,5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3 ′, 4,4 ′, 5,5′-hexahydroxybenzophenone— 1,2-naphthoquinone diazide sulfonic acid esters of hexahydroxybenzophenones such as 1,2-naphthoquinone diazide-5-sulfonic acid ester; bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone diazide-4- Sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2 Naphthoquinonediazide-5-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfone Acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2- Naphthoquinonediazide-5-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane- 1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2′-bis (2 3,4-Trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2′-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5 -Sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-Dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] ] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 ′ -[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4 -Hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide -5-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,5', 6,6 ', 7,7'-hexanol-1,2- Naphthoquinonediazide-4-sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,5 ′, 6,6 ′ 7,7′-hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfone 1,2-naphtho of (polyhydroxyphenyl) alkanes such as acid esters, 2,2,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonate And quinonediazide sulfonic acid esters. From the viewpoint of dissolution inhibiting ability, 1,2-naphthoquinone diazide sulfonic acid esters are preferable, 1,2-naphthoquinone diazide-4-sulfonic acid esters, and 1,2-naphthoquinone diazide-5-sulfonic acid esters are photosensitive. More preferable from the viewpoint of contrast. Among these, a compound represented by the following general formula (17) (Q is a structure represented by the formula (18) or a hydrogen atom) is particularly preferable.

  As a photosensitizer, the compound b described later refers to a compound having an average of 2.9 of the three Qs in the general formula (17) having a structure represented by the general formula (18).

  The amount of the positive photosensitive agent in the photosensitive resin composition is preferably 1 part by mass or more and 50 parts by mass or less, more preferably from the viewpoint of photosensitive contrast, when the amount of the polyimide precursor is 100 parts by mass. 5 parts by mass or more and 30 parts by mass or less. If it is 1 mass part or more, since there exists a tendency for dissolution suppression of an unexposed part to be enough, it is preferable. If it is 50 mass parts or less, since it exists in the tendency for a sensitivity to be high enough, it is preferable.

  In the photosensitive resin composition of the present invention, a compound having reactivity with a thermosetting resin and a polyimide precursor for the purpose of improving the toughness, solvent resistance and heat resistance (thermal stability) of the film after baking. , At least one compound selected from the group consisting of:

  Examples of the thermosetting resin include epoxy resins, cyanate ester resins, unsaturated polyester resins, benzoxazine resins, benzoxazolines, phenol resins, melamine resins, maleimide compounds, and blocked isocyanates.

  Examples of the compound having reactivity with the polyimide precursor include a compound capable of reacting with a carboxyl group, amino group or terminal acid anhydride in a polymer to form a three-dimensional crosslinked structure. Among them, a so-called thermal base generator compound that generates an amino group as a base by heating is preferable. For example, it can be obtained by protecting the amino group of a base compound such as an amine with an acid chloride compound, which forms a salt structure with an acid such as sulfonic acid, is protected with a dicarbonate compound. Thereby, it is stable without exhibiting basicity at room temperature, and can be a thermal base generator that generates a base by deprotection by heating.

  The addition amount of at least one compound selected from the group consisting of a thermosetting resin and a compound reactive with the polyimide precursor is from the viewpoint of developability when the amount of the polyimide precursor is 100 parts by mass. 50 mass parts or less are preferable and 40 mass parts or less are more preferable.

(D) Phosphorus compound It is preferable that the photosensitive resin composition contains (D) a phosphorus compound. A phosphorus compound will not be limited if it is a compound which contains a phosphorus atom in a structure. Examples of such compounds include phosphate ester compounds and phosphazene compounds.

  Examples of phosphoric acid ester compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, triisobutyl phosphate, phosphate ester having tris (2-ethylhexyl) phosphate as a substituent, tris (butoxyethyl) phosphate, etc. Phosphorus ester, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, resorcinol bis (diphenyl phosphate) and other aromatic organic groups as substituents Examples include acid ester compounds. Among these, tris (butoxyethyl) phosphate and triisobutyl phosphate are preferable from the viewpoint of developability.

  Examples of the phosphazene compound include structures represented by the following general formula (19) and the following general formula (20).

R ₃₄ , R ₃₅ , R ₃₆ , and R ₃₇ in the phosphazene compound represented by the general formula (19) and the general formula (20) are not limited as long as they are organic groups having 1 to 20 carbon atoms. A carbon number of 1 or more is preferable because flame retardancy tends to be exhibited. A carbon number of 20 or less is preferred because it tends to be compatible with the polyimide precursor. Among these, a functional group derived from an aromatic compound having 6 to 18 carbon atoms is particularly preferable from the viewpoint of flame retardancy. As such a functional group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2-cyanophenyl Group, functional group having a phenyl group such as 3-cyanophenyl group and 4-cyanophenyl group, functional group having a naphthyl group such as 1-naphthyl group and 2-naphthyl group, pyridine, imidazole, triazole, tetrazole and the like. And functional groups derived from nitrogen heterocyclic compounds. These compounds may be used alone or in combination of two or more as required. Among these, a compound having a phenyl group, a 3-methylphenyl group, a 4-hydroxyphenyl group, and a 4-cyanophenyl group is preferable because of availability.

  V in the phosphazene compound represented by the general formula (19) is not limited as long as it is 3 or more and 25 or less. When it is 3 or more, flame retardancy is exhibited, and when it is 25 or less, the solubility in an organic solvent is high. Among these, it is preferable that v is 3 or more and 10 or less because of availability.

  The w in the phosphazene compound represented by the general formula (20) is not limited as long as it is 3 or more and 10,000 or less. When it is 3 or more, flame retardancy is exhibited, and when it is 10,000 or less, the solubility in organic solvents is high. Among these, 3 or more and 100 or less are preferable in view of availability.

D and E in the phosphazene compound represented by the general formula (20) are not limited as long as they are organic groups having 3 to 30 carbon atoms. In this, D is _{-N = P (OC 6 H 5} ) 3, -N = P (OC 6 H 5) 2 (OC 6 H 4 OH), - N = P (OC 6 H 5) (OC 6 _{H 4 OH) 2, -N =} P (OC 6 H 4 OH) 3, -N = P (O) (OC 6 H 5), - N = P (O) (OC 6 H 4 OH) are preferred.

E is _{-P (OC 6 H 5) 4} , -P (OC 6 H 5) 3 (OC 6 H 4 OH), - P (OC 6 H 5) 2 (OC 6 H 4 OH) 2, -P ( _{OC 6 H 5) (OC 6} H 4 OH) 3, -P (OC 6 H 4 OH) 4, -P (O) (OC 6 H 5) 2, -P (O) (OC 6 H 4 OH) _2, such as _{-P (O) (OC 6 H} 5) (OC 6 H 4 OH) are preferred.

  In the photosensitive resin composition, the addition amount of the phosphorus compound is preferably 50 parts by mass or less from the viewpoint of developability and the like when the amount of the polyimide precursor is 100 parts by mass. From the viewpoint of flame retardancy of the cured product, 45 parts by mass or less is preferable, and 40 parts by mass or less is more preferable. In addition, you may use a phosphorus compound in 1 type or in combination of 2 or more types.

  The photosensitive resin composition can contain other compounds as long as the performance is not adversely affected. Specific examples thereof include heterocyclic compounds for improving adhesion and pigments and dyes for coloring the film.

  The heterocyclic compound is not limited as long as it is a cyclic compound containing a hetero atom. Here, the hetero atom in the present invention includes oxygen, sulfur, nitrogen, and phosphorus. Specific examples include 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, imidazole such as 2-phenylimidazole, N-alkyl group-substituted imidazole such as 1,2-dimethylimidazole, Aromatic group-containing imidazole such as 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl Imidazole compounds such as 2-undecylimidazole, cyano group-containing imidazoles such as 1-cyanoethyl-2-phenylimidazole, silicon-containing imidazoles such as imidazolesilane, 5-methylbenzotriazole, 1- (1 ′, 2′-dica Bo carboxyethyl benzotriazole), triazole compounds such as 1- (2-ethyl-F carboxymethyl aminomethyl benzotriazole), etc. oxazole compounds 2-methyl-5-phenyl-benzoxazole and the like. Examples of pigments and dyes include phthalocyanine compounds.

  The addition amount of other compounds is not limited as long as it is 0.01 part by mass or more and 30 parts by mass or less. If it is 0.01 mass part or more, there exists a tendency for adhesiveness and the coloring property to a film to fully improve, and if it is 30 mass parts or less, there will be no bad influence on photosensitivity.

  The photosensitive resin composition may optionally contain an organic solvent. The organic solvent is not limited as long as it can uniformly dissolve and / or disperse the polyimide precursor. Examples of such organic solvents include dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and other ether compounds having 2 to 9 carbon atoms; acetone, methyl ethyl ketone A ketone compound having 2 to 6 carbon atoms; a saturated hydrocarbon compound having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, and decalin; benzene, toluene, Aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as xylene, mesitylene and tetralin; methyl acetate, ethyl acetate, γ-butyrolactone, benzo Ester compounds having 3 to 9 carbon atoms such as methyl acid; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride and 1,2-dichloroethane; acetonitrile, N, N-dimethyl Examples thereof include nitrogen-containing compounds having 2 to 10 carbon atoms such as formamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; and sulfur-containing compounds such as dimethyl sulfoxide.

  These may be one kind or a mixture of two or more kinds as necessary. Particularly preferable organic solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 9 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and 2 to carbon atoms. The nitrogen-containing compound of 10 or less is mentioned.

  Moreover, 1 type or 2 or more types of mixtures may be sufficient as needed. From the viewpoint of solubility of the polyimide precursor, triethylene glycol dimethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, and N, N-dimethylacetamide are preferable.

  The density | concentration of the polyimide precursor in the resin composition which consists of a polyimide precursor and an organic solvent will not be restrict | limited especially if it is a density | concentration which can synthesize | combine a resin molding. The concentration of the polyimide precursor is preferably 1% by mass or more from the viewpoint of the film thickness of the resin molded body to be produced, and the concentration of the polyimide precursor is preferably 90% by mass or less from the uniformity of the film thickness of the resin molded body. From the viewpoint of the film thickness of the obtained resin molding, it is more preferably 2% by mass or more and 80% by mass or less.

<Photosensitive film>
The photosensitive resin composition can be suitably used for a photosensitive film. From the viewpoint of producing a photosensitive film, the concentration of the polyimide precursor in the photosensitive resin composition is preferably 1% by mass or more and 90% by mass or less. The concentration of the polyimide precursor is preferably 1% by mass or more from the viewpoint of the film thickness of the photosensitive film, and preferably 90% by mass or less from the viewpoint of the viscosity and film thickness uniformity of the photosensitive resin composition. From a viewpoint of the film thickness of the obtained photosensitive film, 2 mass% or more and 80 mass% or less are more preferable.

Next, the manufacturing method of a photosensitive film is demonstrated.
First, the substrate is coated with the photosensitive resin composition. As a base material, if it is a base material which is not damaged in the case of photosensitive dry film formation, it will not be limited. Examples of such a substrate include a silicon wafer, glass, ceramic, heat resistant resin, and carrier film. Examples of the carrier film include a polyethylene terephthalate film and a metal film. A heat-resistant resin and a carrier film are preferable from the viewpoint of easy handling, and a polyethylene terephthalate film is particularly preferable from the viewpoint of peelability after pressure bonding to the substrate.

  Examples of the coating method include bar coating, roller coating, die coating, blade coating, dip coating, doctor knife, spray coating, flow coating, spin coating, slit coating, and brush coating. After coating, if necessary, heat treatment called pre-baking may be performed with a hot plate or the like.

  Thus, when using the photosensitive film comprised by the photosensitive resin composition, after apply | coating the solution of the photosensitive resin composition on arbitrary base materials by arbitrary methods, it is made into a dry film, for example, a carrier. It is set as the laminated film which has a film and a photosensitive film.

  Moreover, it is good also as a laminated | multilayer film by providing at least one layer of arbitrary antifouling and protective cover films on a photosensitive film. In the laminated film according to the present invention, the cover film is not limited as long as it is a film that protects a photosensitive film such as low-density polyethylene.

  Next, a flexible printed wiring board can be obtained by pressure-bonding the photosensitive film to a substrate having wiring so as to cover the wiring, performing alkali development, and firing.

  Examples of the substrate having wiring in the flexible printed wiring board include a hard substrate such as a glass epoxy substrate and a glass maleimide substrate, or a flexible substrate such as a copper-clad laminate. Among these, a flexible substrate is preferable from the viewpoint of bendability.

  In the formation method of the said flexible printed wiring board, if a photosensitive film is formed in a base material so that wiring may be covered, it will not be limited. Examples of such a forming method include a method of performing hot pressing, thermal laminating, thermal vacuum pressing, thermal vacuum laminating and the like in a state where the wiring side of the substrate having wiring and the photosensitive film are in contact with each other. Among these, from the viewpoint of embedding the photosensitive film between the wirings, a heat vacuum press or a heat vacuum laminate is preferable.

  The heating temperature at the time of laminating the photosensitive film on the substrate having wiring is not limited as long as the photosensitive film can adhere to the substrate. From the viewpoint of adhesion to the substrate and from the viewpoint of decomposition of the photosensitive film and side reactions, 30 ° C. or more and 400 ° C. or less are preferable. More preferably, it is 50 degreeC or more and 150 degrees C or less.

  The surface treatment of the substrate having wiring is not particularly limited, and examples thereof include hydrochloric acid treatment, sulfuric acid treatment, and sodium persulfate aqueous solution treatment.

  In the case of a positive type, the photosensitive film can be subjected to positive type photolithography by dissolving the light irradiation site by alkali development after light irradiation. In the case of the negative type, negative photolithography can be performed by dissolving the portion other than the light irradiation portion by alkali development after the light irradiation. In this case, examples of the light source used for light irradiation include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, a tungsten lamp, an argon laser, and a helium cadmium laser. Among these, a high pressure mercury lamp and an ultrahigh pressure mercury lamp are preferable.

  The alkaline aqueous solution used for development is not limited as long as it is a solution that can dissolve the light irradiation site in the case of the positive type, and other than the light irradiation site in the case of the negative type. Examples of such a solution include a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, and a tetramethylammonium hydroxide aqueous solution. From the viewpoint of developability, an aqueous sodium carbonate solution and an aqueous sodium hydroxide solution are preferred. Examples of the development method include spray development, immersion development, and paddle development.

  Next, the printed wiring board is formed by firing the printed wiring board to which the photosensitive film is pressure-bonded. Firing is preferably carried out at a temperature of 30 ° C. or higher and 400 ° C. or lower from the viewpoints of solvent removal, side reactions and decomposition. More preferably, it is 100 degreeC or more and 300 degrees C or less.

  The reaction atmosphere in the firing can be performed in an air atmosphere or an inert gas atmosphere. In the production of a printed wiring board, the time required for firing varies depending on the reaction conditions, but is usually within 24 hours, and particularly preferably in the range of 1 to 8 hours.

  Since the photosensitive resin composition in the present invention has good warping after curing, good developability, and exhibits flame retardancy and good insulation reliability after firing, various electronic devices in the electronics field Protective layer formation for printed wiring boards and circuit boards used for operation panels, etc., insulating layer formation for laminated substrates, silicon wafers used in semiconductor devices, semiconductor chips, semiconductor device peripheral members, semiconductor mounting substrates, heat dissipation It is used for film formation on electronic parts for use in protection, insulation and adhesion of plates, lead pins, semiconductors, etc. A protective film that protects wiring formed on a silicon wafer, a copper clad laminate, a printed wiring board, or the like is called a coverlay.

  Phosphorus atom-containing polyimide precursors and photosensitive resin compositions are obtained by imidization for flexible printed circuit (FPC) substrates, tape automation bonding (TAB) substrates, electrical insulating films and liquid crystal displays in various electronic devices. It can be suitably used for a substrate, a substrate for organic electroluminescence (EL) display, a substrate for electronic paper, a substrate for solar cell, particularly a coverlay for a flexible printed wiring circuit. Moreover, it can also be used as a laminated body provided with the coverlay and the copper clad laminated board.

(Example)
Next, examples performed for clarifying the effects of the present invention will be described.

<Reagent>
In Examples and Comparative Examples, TMEG (trade name: TMEG-100 (manufactured by Shin Nippon Chemical Co., Ltd.)), APB (trade name: APB-N (manufactured by Mitsui Chemicals)), Jeffamine (trade name) are used reagents. : Jeffamine XTJ-542 (manufactured by Huntsman), silicone diamine (manufactured by Shin-Etsu Chemical Co., Ltd., KF-8010), phosphazene compound (trade name: FP-390, manufactured by Fushimi Pharmaceutical Co., Ltd.), EO-modified bisphenol A dimethacrylate (trademark) Name: BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.)), pentaerythritol tri / tetra (meth) acrylate (trade name: Aronix M-306 (manufactured by Toagosei Co., Ltd.), ethanone 1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (trade name: IRGACURE OX E 02 (manufactured by Ciba Japan), toluene (manufactured by Wako Pure Chemical Industries, for organic synthesis), γ-butyrolactone (manufactured by Wako Pure Chemical Industries), triethylene glycol dimethyl ether (manufactured by Wako Pure Chemical Industries), carbonic acid Sodium (manufactured by Wako Pure Chemical Industries, Ltd.), 1,2-naphthoquinonediazide-5-sulfonic acid ester (trade name: PA-6, manufactured by Daito Chemix Co., Ltd.) Compound b, phosphorus atom-containing tetracarboxylic dianhydride (described below) General formula (21), hereinafter abbreviated as TAPQ (manac), and tris (butoxyethyl) phosphate (hereinafter abbreviated as TBEP) were used without any special purification.

<Weight average molecular weight measurement>
Gel permeation chromatography (GPC), which is a method for measuring the weight average molecular weight, was measured under the following conditions. N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) was used as a solvent, and 24.8 mmol / L lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity before measurement). 99.5%) and 63.2 mmol / L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) were used.
Column: Shodex KD-806M (manufactured by Showa Denko KK)
Flow rate: 1.0 mL / min Column temperature: 40 ° C
Pump: PU-2080 Plus (manufactured by JASCO)
Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO)
UV-2075 Plus (UV-VIS: UV-Visible Absorber, manufactured by JASCO)
A calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).

<Film thickness measurement>
The film thickness of the cured body was measured using a film thickness meter (ID-C112B, manufactured by Mitutoyo).

<Dry film manufacturing method>
The coating method of the photosensitive resin composition was performed by a doctor blade method using FILMCOATER (manufactured by TESTER SANGYO, PI1210). The said photosensitive resin composition was dripped at PET film (Teijin DuPont Films make, N152Q), and it coat | coated with the clearance of 150 micrometers. The coated film was dried at 95 ° C. for 30 minutes using a dryer (SPHH-10L, manufactured by ESPEC) to obtain a photosensitive dry film.

<Lamination conditions>
Lamination in the present invention was performed using a vacuum press (manufactured by Meiki Seisakusho). The press temperature was 70 ° C. to 100 ° C., the press pressure was 0.5 MPa, and the press time was 30 seconds to 60 seconds.

<Developability evaluation>
In the evaluation of developability, after laminating on a copper-clad laminate using a photosensitive dry film under the above-mentioned laminating conditions, in the case of a positive photosensitive resin composition, a positive mask is used to apply a dose of 1. Exposure is carried out at 0 J / cm ² , and in the case of a negative photosensitive resin composition, exposure is carried out at 30 mJ / cm ² -270 mJ / cm ² , followed by alkaline development treatment with 1% by mass sodium carbonate aqueous solution and water The pattern was rinsed, and after drying, the pattern was evaluated with an optical microscope. A circular pattern having a 100 μm diameter (interval of 100 μm pitch) was used as the mask. By development, in the case of positive type, the copper surface appears in the exposed portion, and in the negative type, the copper surface appears in the unexposed portion and the remaining film ratio is 75% or more. The case where the resolution was inferior or the film thickness was less than 75% was evaluated as x.

<Measurement of warpage after firing>
The obtained photosensitive dry film was laminated on Kapton (registered trademark) under the above-mentioned lamination conditions, and then baked at 120 ° C. for 1 hour and then at 180 ° C. for 1 hour. The film was cut into 5 cm squares, and those having a floating height of 10 mm or less at the end were marked with ◯, and those having a floating height above that were marked with ×.

<Flame retardance test>
The flame retardancy evaluation was carried out on a polyimide film (Kapton EN-100 trade name, manufactured by Toray DuPont) using a photosensitive dry film under the above laminating conditions, followed by 1 hour at 120 ° C., followed by 180 Firing was carried out at a temperature of 1 hour.

  The obtained film was cut to a width of 1 cm and a length of 4 cm. Next, the process of igniting one end of the test piece and spreading it was visually observed. A sample that was extinguished during the course was marked with ◯, and a sample that had all burned was marked with ×.

<Synthesis of thermal base generator 1>
The synthesis of the thermal base generator 1 in the present invention was performed as follows.
3,4′-Diaminodiphenyl ether (250 mmol) was dissolved in tetrahydrofuran (140 g), and a tetrahydrofuran solution of di-t-butyl dicarbonate (550 mmol) was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was stirred at 50 ° C. for 5 hours, cooled to room temperature, the reaction solution was poured into distilled water (1000 g), and the precipitated solid was extracted three times with ethyl acetate (300 mL), followed by the organic layer. Was washed 3 times with 5 mass% aqueous sodium hydrogen carbonate solution (200 mL), washed 3 times with distilled water (200 mL), dried over magnesium sulfate, and concentrated under reduced pressure to give a white solid. This solid was recrystallized from an ethanol-hexane mixed solvent to obtain a hot base generator 1.

[Example 1]
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with silicone diamine (KF-8010) (12.7 mmol), γ-butyrolactone (28 g), triethylene glycol dimethyl ether (12 g), TMEG (18 mmol), TAPQ (2 mmol) and toluene (20 g) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., subsequently APB-N (7.25 mmol) was added, and the mixture was stirred at 25 ° C. for 5 hours to obtain a solution of a polyimide precursor (1). The weight average molecular weight and C / (A + B + C) are shown in Table 1 below.

  Next, PA-6 (20 parts by mass) and TBEP (10 parts by mass) were mixed with 100 parts by mass of the polyimide precursor (1) to prepare a photosensitive resin composition. The photosensitive resin composition was evaluated for alkali developability in a 1% by mass aqueous sodium carbonate solution, flame retardancy test, and warpage of the film after firing. The results are shown in Table 2 below.

[Example 2]
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with silicone diamine (KF-8010) (13.7 mmol), γ-butyrolactone (28 g), triethylene glycol dimethyl ether (12 g), TMEG (14 mmol), TAPQ (6 mmol) and toluene (20 g) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., subsequently APB-N (6.3 mmol) was added, and the mixture was stirred at 25 ° C. for 5 hours to obtain a solution of a polyimide precursor (2). The weight average molecular weight and C / (A + B + C) are shown in Table 1 below.

  Next, PA-6 (20 parts by mass) and TBEP (10 parts by mass) were mixed with 100 parts by mass of the polyimide precursor (2) to prepare a photosensitive resin composition. The photosensitive resin composition was evaluated for alkali developability in a 1% by mass aqueous sodium carbonate solution, flame retardancy test, and warpage of the film after firing. The results are shown in Table 2 below.

[Example 3]
In a nitrogen atmosphere, a separable flask equipped with a Dean-Stark apparatus and a refluxer was charged with Jeffamine (XTJ-542) (10 mmol), γ-butyrolactone (35 g), triethylene glycol dimethyl ether (15 g), TMEG (32.9 mmol), TAPQ (3.72 mmol) and toluene (20 g) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., APB-N (25 mmol) was subsequently added, and the mixture was stirred at 25 ° C. for 5 hours to obtain a solution of a polyimide precursor (3). The weight average molecular weight and the evaluation results of Z / (X + Y + Z) thermal stability are shown in Table 1 below.

  Next, with respect to 100 parts by mass of the polyimide precursor (3), BPE-500 (30 parts by mass), M-306 (5 parts by mass), IRGACURE OXE 02 (in Table 1, expressed as IRGACURE, the same applies hereinafter) ( 1 part by mass) and FP-390 (20 parts by mass) were mixed to prepare a photosensitive resin composition. The photosensitive resin composition was evaluated for alkali developability in a 1% by mass aqueous sodium carbonate solution, flame retardancy test, and warpage of the film after firing. The results are shown in Table 2 below.

[Example 4]
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a reflux was added to Jeffamine (XTJ-542) (9.5 mmol), γ-butyrolactone (35 g), triethylene glycol dimethyl ether (15 g), TMEG (22.7 mmol). ), TAPQ (9.7 mmol) and toluene (20 g) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., subsequently APB-N (22.6 mmol) was added, and the mixture was stirred at 25 ° C. for 5 hours to obtain a solution of a polyimide precursor (4). The weight average molecular weight and Z / (X + Y + Z) are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), and FP-390 (20 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (4). The photosensitive resin composition was prepared. The photosensitive resin composition was evaluated for alkali developability in a 1% by mass aqueous sodium carbonate solution, flame retardancy test, and warpage of the film after firing. The results are shown in Table 2 below.

[Example 5]
BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-390 (20 parts by mass), heat with respect to 100 parts by mass of the polyimide precursor (4) Base generator 1 (2.5 parts by mass) was mixed to prepare a photosensitive resin composition. The photosensitive resin composition was evaluated for alkali developability in a 1% by mass aqueous sodium carbonate solution, flame retardancy test, and warpage of the film after firing. The results are shown in Table 2 below.

[Comparative Example 1]
In a nitrogen atmosphere, a separable flask equipped with a Dean-Stark apparatus and a refluxer was charged with silicone diamine (12.2 mmol), γ-butyrolactone (35 g), triethylene glycol dimethyl ether (15 g), TMEG (20 mmol), and toluene (20 g). The mixture was heated to 180 ° C. and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., subsequently APB-N (7.6 mmol) was added, and the mixture was stirred at 25 ° C. for 5 hours to obtain a solution of a polyimide precursor (5). The weight average molecular weight and C / (A + B + C) are shown in Table 1 below.

  PA-6 (20 parts by mass) and TBEP (10 parts by mass) were mixed with 100 parts by mass of the polyimide precursor to prepare a photosensitive resin composition. The photosensitive resin composition was evaluated for alkali developability in a 1% by mass aqueous sodium carbonate solution, flame retardancy test, and warpage of the film after firing. The results are shown in Table 2 below.

[Comparative Example 2]
Under a nitrogen atmosphere, γ-butyrolactone (35 g), triethylene glycol dimethyl ether (15 g), toluene (20 g), Jeffamine XTJ542 (10 mmol), and TMEG (39.0 mmol) were placed in a separable flask and heated to 180 ° C. And stirred at 180 ° C. for 1 hour. After removing toluene which is an azeotropic solvent, the mixture was cooled to 25 ° C., then APB-N (25.5 mmol) was added, and the mixture was stirred at 25 ° C. for 5 hours, then stirred at 25 ° C. for 8 hours. A solution was obtained. The weight average molecular weight, Z / (X + Y + Z), and thermal stability evaluation results are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (5 parts by mass), IRGACURE OXE 02 (1 part by mass), and FP390 (20 parts by mass) are mixed with 100 parts by mass of the polyimide precursor. A resin composition was prepared. The photosensitive resin composition was evaluated for alkali developability in a 1% by mass aqueous sodium carbonate solution, flame retardancy test, and warpage of the film after firing. The results are shown in Table 2 below.

  From the results of Table 2, when the polyimide precursors according to the present invention (Examples 1 to 5) are used, the developability and warpage are better than those of Comparative Examples 1 and 2, and flame retardancy is improved. It turns out that it expresses.

  The photosensitive resin composition of the present invention includes a surface protective film for a semiconductor device, an interlayer insulating film, an insulating film for rewiring, a protective film for a device having a bump structure, an interlayer insulating film for a multilayer circuit, and a cover for a flexible copper-clad plate It can be suitably used as a coat and a liquid crystal alignment film.

Claims (17)

It is a polyimide precursor containing a phosphorus atom, and has a polyimide structure represented by the following general formula (1) and a polyamic acid structure represented by the following general formula (2) as repeating structural units, respectively. Characteristic polyimide precursor.

(-T- in Formula (1) represents General Formula (3) and / or General Formula (4). In Formula (1), Formula (2), Formula (3), and Formula (4), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ₃ , R ₆ , R ₉ , R ₁₂ , and R ₁₅ represent a tetravalent organic group having 1 to 20 carbon atoms, and m, n, and p are respectively Independently represents an integer of 0 to 100. R ₁₆ represents a tetravalent organic group derived from tetracarboxylic dianhydride, and R ₁₇ represents a divalent organic group having 1 to 90 carbon atoms. , R ₁₆ and / or R ₁₇ contain a phosphorus atom, R ₁₈ is a divalent organic group having 1 to 30 carbon atoms, and R ₁₉ is 1 having 1 to 30 carbon atoms. A valent organic group, q represents an integer of 1-30.) The polyimide precursor according to claim 1, comprising a structure represented by the following general formula (5).

(In the formula (5), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ are each independently a hydrogen atom or carbon number 1 to carbon number. Represents a monovalent organic group of 20, which may be the same or different, and R ₃ , R ₆ , R ₉ , R ₁₂ , and R ₁₅ represent a tetravalent organic group having 1 to 20 carbon atoms. M, n and p each independently represents an integer of 0 to 100. R ₁₆ represents a tetravalent organic group derived from tetracarboxylic dianhydride, and R ₁₇ represents a carbon number of 1 to carbon. 90 represents a divalent organic group of 90, R ₁₆ and / or R ₁₇ contains a phosphorus atom, A, B, and C represent mol% of each unit, and 0.05 ≦ C / (A + B + C) ≦ 0. 95 is satisfied.) The polyimide precursor according to claim 1, comprising a structure represented by the following general formula (6).

(In the formula (6), R ₁₆ is a tetravalent organic group having 1 to 50 carbon atoms derived from tetracarboxylic dianhydride, R ₁₈ is a divalent organic group having 1 to 30 carbon atoms, R ₁₇ is a divalent organic group having 1 to 90 carbon atoms, R ₁₉ is a monovalent organic group having 1 to 30 carbon atoms, q is an integer of 1 to 30, and R ₁₆ and / or R ₁₇ contains a phosphorus atom, and X, Y, and Z represent mol% of each unit and satisfy 0.05 ≦ Z / (X + Y + Z) ≦ 0.95.) The polyimide precursor according to any one of claims 1 to 3, comprising an acid dianhydride represented by the following general formula (7) and / or the following general formula (8).

(In Formula (7) and Formula (8), R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Ar represents 5 or more carbon atoms. Represents a divalent organic group derived from an aromatic compound having 20 or less carbon atoms.) The polyimide precursor according to any one of claims 1 to 4, comprising at least one diamine selected from the group consisting of the following general formula (9) to the following general formula (13).

(In the formulas (9) to (13), R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ are a hydrogen atom or a carbon number 1 to 1 Represents a monovalent organic group having 20 carbon atoms.)   A photosensitive resin composition comprising the polyimide precursor according to claim 1 and a photosensitive agent.   The said photosensitive agent contains the (meth) acrylate compound which has at least 2 unsaturated double bond which can be photopolymerized, and a photoinitiator, The photosensitive resin composition of Claim 6 characterized by the above-mentioned. .   The (meth) acrylate compound having at least two unsaturated double bonds capable of photopolymerization includes both a compound having two double bonds and a compound having three or more double bonds. Item 8. The photosensitive resin composition according to Item 7.   The photosensitive resin composition according to claim 6, wherein the photosensitive agent is a quinonediazide compound.   The photosensitive resin composition according to claim 6, comprising a phosphorus compound.   The photosensitive resin composition according to claim 10, wherein the phosphorus compound has at least one structure selected from the group consisting of a phosphate ester structure and a phosphazene structure.   A photosensitive film comprising the photosensitive resin composition according to claim 6 and a support film layer.   13. The photosensitive film according to claim 12, comprising a carrier film on the entire surface of one side.   The photosensitive film according to claim 13, further comprising a cover film.   The coverlay obtained by imidating the photosensitive resin composition in any one of Claims 6-11.   A flexible printed wiring board obtained by imidizing the photosensitive resin composition according to any one of claims 6 to 11 on a substrate having wiring.   A laminate comprising the coverlay according to claim 15 and a copper clad laminate.